CN101985493A - Preparation method of cyhalothrin molecularly imprinted polymer and use thereof - Google Patents
Preparation method of cyhalothrin molecularly imprinted polymer and use thereof Download PDFInfo
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- CN101985493A CN101985493A CN 201010268194 CN201010268194A CN101985493A CN 101985493 A CN101985493 A CN 101985493A CN 201010268194 CN201010268194 CN 201010268194 CN 201010268194 A CN201010268194 A CN 201010268194A CN 101985493 A CN101985493 A CN 101985493A
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- cyhalothrin
- lambda
- molecularly imprinted
- imprinted polymer
- cyclodextrin
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- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ZXQYGBMAQZUVMI-UNOMPAQXSA-N cyhalothrin Chemical compound CC1(C)C(\C=C(/Cl)C(F)(F)F)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-UNOMPAQXSA-N 0.000 title abstract description 8
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 27
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 20
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 20
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 20
- 229960004853 betadex Drugs 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- -1 isocyanate compound Chemical class 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 238000002137 ultrasound extraction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 230000007613 environmental effect Effects 0.000 claims abstract 2
- ZXQYGBMAQZUVMI-RDDWSQKMSA-N (1S)-cis-(alphaR)-cyhalothrin Chemical compound CC1(C)[C@H](\C=C(/Cl)C(F)(F)F)[C@@H]1C(=O)O[C@@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-RDDWSQKMSA-N 0.000 claims description 83
- 239000005910 lambda-Cyhalothrin Substances 0.000 claims description 83
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000006228 supernatant Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 13
- 239000006210 lotion Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
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- 229920000642 polymer Polymers 0.000 abstract description 16
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- 238000011084 recovery Methods 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
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- 230000006870 function Effects 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
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- 230000000694 effects Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
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- 230000002950 deficient Effects 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
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- 239000003905 agrochemical Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
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- 235000014347 soups Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention discloses a preparation method of cyhalothrin molecularly imprinted polymer, orderly including the following steps: 1) dissolving a beta-cyclodextrin as functional monomers in a solvent, and then, adding a cyhalothrin as molecular templates for stirred reaction at room temperature; 2) adding a isocyanate compound as a cross-linking agent in a mixed liquor obtained from the step 1) for reaction with magnetic stirring; 3) washing the reaction products of the step 2) with an ultrasonic extraction method to remove the cyhalothrin, the un-reacted beta-cyclodextrin, the isocyanate compound and the solvent; 4) processing products of the step 3) with centrifugation, vacuum filtering and drying, and milling the obtained blocky high polymers into grains which are the cyhalothrin molecularly imprinted polymers. The cyhalothrin molecularly imprinted polymers can be used for High-selectivity enrichment and separation and purification of trace amount of the cyhalothrin in environmental samples or plant samples.
Description
Technical field
The present invention relates to a kind of lambda-cyhalothrin molecularly imprinted polymer based on the Subjective and Objective clathration, this polymkeric substance is applicable to the high-selectivity enrichment and the separation and purification of trace lambda-cyhalothrin in environment and the plant sample.
Background technology
(commodity are called cyhalothrin to lambda-cyhalothrin, lambda-cyhalothrin) be (S)-alcohol-(Z)-1R-cis-acid with (R)-alcohol-(Z)-1S-cis-acid[1: 1] mixture, it is as typical s-generation pyrethroid pesticide, have that insecticidal action is fast, the lasting period is long, the characteristics of efficient, low toxicity and low residue, is that one of principal item of mite is killed in current domestic and international farming, forestry deinsectization.It to be to tag and stomach poison function, perviousness is arranged and does not have systemic action, can prevent and treat lepidopteran, Hemiptera, Coleoptera and mite pest effectively, but to the high poison of hydrocoles such as fishes and shrimps, silkworm and honeybee.Some toxicity reports about lambda-cyhalothrin are also arranged so far, as there are some researches show that lambda-cyhalothrin might cause the sexual function imbalance of male rat; Also have scholar's latest find lambda-cyhalothrin to have the potential neurotoxicity.Because the long-term of lambda-cyhalothrin is extensive use of, its residue problem in agricultural-food and environment is subjected to people's attention day by day.The main detection method of this medicine is a vapor-phase chromatography at present, though method sensitivity is higher, the sample pre-treatments step is more, wastes time and energy relatively, especially the retention analysis in the complex matrices sample.Therefore, this just need seek determinand is had the pre-treatment purifying method of highly selective.
Molecular imprinting has been considered to prepare the effective means of highly selective separating medium.As new functional macromolecule material, and molecularly imprinted polymer (molecularly imprinted polymer, MIP) with the separating or analyze medium and compare of routine, its outstanding advantage is that separated object or analyte are had higher selectivity and affinity; Compare with biological active materials, have easy to prepare, better tolerance again, characteristics such as can reuse.
So far, most of synthetic agricultural chemicals MIPs can only effectively discern in low polar organic phase system, this be since hydrogen bond as the most common reactive force in the non-covalent blotting, be subjected to the interference of water and polar solvent bigger, therefore be difficult to realize the specific recognition function of aqueous phase MIPs target analytes.Compare with traditional conventional func monomer (as acrylic acid or the like), cyclodextrin and derivative thereof are proved to be a kind of function monomer of some MIPs in the identification selection of aqueous phase that be expected to improve.Common cyclodextrin is respectively by α-1 by 6,7,8 α-D-glucopyranose units, the α that 4 glycosidic links are formed by connecting-, β-, γ-Huan Hujing, because its structure has the characteristics of " outer is hydrophilic, inner chamber is hydrophobic ", can form stable inclusion compound with multiple guest molecule, the research in fields such as chiral material fractionation, environmental pollutant monitoring, pharmaceutical analysis increases day by day.Existing research (Hishiya, T.; Shibata, M.; Kakazu, M.; Et al., Molecularly imprinted cyclodextrins asselective receptors for steroids.Macromolecules 1999,32, (7), 2265-2269) show, utilize the Subjective and Objective clathration, cyclodextrin is introduced the molecular imprinting process as function monomer, can realize the specificity bonding of beta-cyclodextrin cross-linked polymer the bigger hydrophobicity template molecule (as cholesterol) of structure.But, cyclodextrin still need be carried out one by one as the research that function monomer prepares corresponding MIP for concrete template molecule; This is because the MIP performance difference that different template molecule participation trace reactions obtains is bigger.And at present, do not see with the cyclodextrin to be the research report that function monomer prepares lambda-cyhalothrin MIP and application thereof as yet in external.In addition, compare other agricultural chemicals, the molecular structure of lambda-cyhalothrin is bigger, polar group seldom, be difficult for producing stronger Intermolecular Forces with conventional function monomer, thereby trace efficient is relatively poor, causes the specific combination performance of the MIP that obtains not ideal enough, and therefore need seeking more suitably, function monomer prepares MIP.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method and its usage of lambda-cyhalothrin molecularly imprinted polymer, the selective enrichment that this lambda-cyhalothrin molecularly imprinted polymer can be used for complex matrices sample trace lambda-cyhalothrin with separate identification.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of lambda-cyhalothrin molecularly imprinted polymer, may further comprise the steps successively:
1), will be dissolved in as the beta-cyclodextrin of function monomer in the solvent, add lambda-cyhalothrin then, stirring reaction 0.5～1.5h under the room temperature as template molecule; The mol ratio of described beta-cyclodextrin and lambda-cyhalothrin is 2～5: 1;
2), in the mixed solution of step 1) gained, add isocyanate ester compound, in 60～70 ℃ of magnetic agitation reaction 22～26h as linking agent; The mol ratio of described isocyanate ester compound and lambda-cyhalothrin is 10～30: 1;
3), to step 2) reaction product of gained adopts the washing of ultrasonic extraction method, to remove lambda-cyhalothrin, unreacted beta-cyclodextrin and isocyanate ester compound and solvent, till the washing lotion supernatant does not detect lambda-cyhalothrin;
4), with the step 3) gained through centrifugal, suction filtration, drying, the block superpolymer of gained is ground to form particle, described particle is the lambda-cyhalothrin molecularly imprinted polymer.
Improvement as the preparation method of lambda-cyhalothrin molecularly imprinted polymer of the present invention: isocyanate ester compound is 1, hexamethylene-diisocyanate, benzene-2,4-vulcabond, Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond or naphthalene diisocyanate.
Further improvement as the preparation method of lambda-cyhalothrin molecularly imprinted polymer of the present invention: the solvent in the step 1) is anhydrous dimethyl sulfoxide (DMSO).
The present invention also discloses the purposes of the lambda-cyhalothrin molecularly imprinted polymer that adopts method for preparing and get simultaneously: be used for the high-selectivity enrichment and the separation and purification of environment and plant sample trace lambda-cyhalothrin.
In step 3) of the present invention, to step 2) reaction product of gained adopts the ultrasonic extraction successively of acetone-hot water-ethanol.Principle is: remove most of template molecule and unreacted linking agent with acetone earlier, reusable heat water (40～60 ℃) is removed most of beta-cyclodextrin and DMSO, removes residual substance with ethanol at last.Till the washing lotion supernatant does not detect lambda-cyhalothrin.
The preparation method of lambda-cyhalothrin molecularly imprinted polymer of the present invention (lambda-cyhalothrin MIP), be to be that template molecule, beta-cyclodextrin are function monomer with the lambda-cyhalothrin, both act on the formation inclusion compound in advance, form cross-linking agent with isocyanate ester compound by polyaddition again, and remove template, thereby obtain molecularly imprinted polymer with eluting solvent.
Lambda-cyhalothrin MIP of the present invention can be used for the high-selectivity enrichment and the separation and purification of environment and plant sample trace lambda-cyhalothrin, be specially: lambda-cyhalothrin MIP is filled in Solid-Phase Extraction (SPE) void column makes the SPE pillar, the extracting solution of sample is carried out purification enrichment with this SPE pillar, with organic solvent and (or) water wash removes interfering substance, and then with organic solvent and (or) water elution, collect elution fraction, detect for chromatogram or immunochemistry.
The lambda-cyhalothrin MIP that the present invention utilizes cyclodextrin to prepare as function monomer, compare with the MIP material (as stated in the Background Art) that uses in the conventional organic phase, it can not only realize that the selectivity to template molecule is discerned in the aqueous phase system, can also improve its specific adsorption capacity to target analytes, and have kinetics in conjunction with fast and the good advantage of regenerability, more be expected to the compatible coupling of itself and multiple detection means (as chemical sensor, GC/HPLC-MS/MS etc.).
Embodiment
Below embodiments of the invention are elaborated.Wherein, for the lambda-cyhalothrin Determination on content, high density adopts high performance liquid chromatography (HPLC), and lower concentration adopts vapor-phase chromatography (GC).
The HPLC condition: C18 chromatographic column (4.6mm * 150mm * 5 μ m) is a moving phase with acetonitrile/water=90/10, and flow velocity 1mL/min, sample size are 20 μ L, and the detection wavelength is 278nm.(limit of detection LOD) is 0.1 μ g/mL to the method minimum detectability.
GC condition: capillary chromatographic column HP-5 (30m * 0.53mm * 0.88 μ m); The injection port gasification temperature is 250 ℃; Electron capture detector (ECD) temperature is 300 ℃; Column temperature heating schedule----starting temperature is 80 ℃ of maintenance 1min, and the speed with 30 ℃/min rises to 220 ℃ then, keeps 0min, and the speed with 10 ℃/min rises to 260 ℃ again, keeps 15min; Sample size is 1 μ L (a not split stream sampling); The make-up gas flow is 30mL/min; Column cap is pressed and is 0.4kg/cm
2Method minimum detectability LOD is 0.005 μ g/mL.
Embodiment 1:
Taking by weighing exsiccant beta-cyclodextrin 1.5mmol is dissolved in the 20ml anhydrous dimethyl sulfoxide (DMSO), add 0.5mmol lambda-cyhalothrin (as template molecule), after room temperature (15～35 ℃) stirs 1h down, slowly drip 1 of 9mmol again, hexamethylene-diisocyanate (HMDI), 65 ℃ of lower magnetic force stirring reaction 24h; After reaction finishes, take out white soup compound, with (the operating frequency of ultrasonic cleaner: of acetone-hot water-ethanol ultrasonic extraction successively 40KHz) to remove template molecule and unreacted beta-cyclodextrin, linking agent (1, hexamethylene-diisocyanate) and DMSO, till the washing lotion supernatant does not detect template molecule (lambda-cyhalothrin).Can adopt the GC method to detect the lambda-cyhalothrin that whether contains in the washing lotion supernatant as template molecule.After centrifugal, suction filtration, the drying bulk polymer is ground to form fine particle, obtain with the crosslinked lambda-cyhalothrin MIP of HMDI (being MIP-HMDI), room temperature preservation is in dry vessel.
(non-imprinted polymer NIP) makes blank, and the synthetic method of non-imprinted polymer is not except that adding the template molecule, and all the other steps are identical with the preparation method of above-mentioned lambda-cyhalothrin MIP, gets NIP-HMDI with non-imprinted polymer.
Measure the particle meso-position radius of crosslinked MIP-HMDI of this beta-cyclodextrin and NIP-HMDI with the laser particle size distribution instrument, be respectively 35.91 μ m and 32.32 μ m.The absorption mean pore size of measuring MIP-HMDI and NIP-HMDI with the lacunarity analysis instrument is 16.1nm and 11.5nm, belongs to the mesopore rank, therefore helps the solute transmission, has improved the speed of polymer scale matched moulds plate molecule.
Experiment 1-1:
Investigate the bonding properties of above-mentioned two kinds of polymkeric substance by batch balance in conjunction with test: take by weighing one group of each 10mg of MIP-HMDI/NIP-HMDI respectively and place the 2ml centrifuge tube respectively to lambda-cyhalothrin, add the lambda-cyhalothrin solution of 1.5ml 5 μ g/ml, this solution is to make solvent with the mixed solution of acetonitrile/water=6: 5 (v/v); The sealing back is room temperature vibration 2h in quiet mixing tank, centrifugal then (8000rpm, 10min), draw an amount of supernatant and cross film (0.22 μ m organic membrane) back direct injection, measure the Cf C of target analytes in the supernatant liquor (being lambda-cyhalothrin solution) with the HPLC method
FreeBefore and after the combination test, the change in concentration of lambda-cyhalothrin in the solution, the absolute bonding properties of calculating polymkeric substance, use in conjunction with per-cent Bound% and weigh:
Bound%=(C
Total-C
Free)/C
Total* 100% (wherein, C
Total: total interpolation concentration of target analytes; C
Frce: in conjunction with the Cf of target analytes in the supernatant of test back); Units of Account quality polymkeric substance is to the binding capacity Q=(C of template molecule then
Total-C
Free) * V/M (wherein, V: the liquor capacity of interpolation; M: the quality that takes by weighing polymkeric substance); Calculation of distribution coefficient (partition coefficient): K=Q/C again
FreeAnd the trace factor (imprinting factor, IF): IF=K
MIP/ K
NIPThe results are shown in Table 1.As can be known from the results, obviously greater than NIP-HMDI, Δ Bound% is about 20% to MIP-HMDI to the binding capacity of template molecule, and IF illustrates that near 2.5 the trace effect is better, and imprinted polymer embodies higher special absorption property.
Experiment 1-2:
Select the blank sample of tap water, soil and wild cabbage respectively, add an amount of lambda-cyhalothrin standard substance stock solution (10 μ g/ml, normal hexane are solvent), specific as follows:
1) water sample: 5ml, adding concentration is 0.02 μ g/ml, directly treats the SPE pillar;
2) soil: 5g, adding concentration is 0.02 μ g/g, adds 10ml acetone and 2ml water earlier, vibration 1h crosses anhydrous sodium sulphate and dewaters centrifuging and taking supernatant liquor 4ml, dry up with nitrogen, finally use the mixed solvent constant volume of 2ml acetonitrile/water=6: 5 (v/v), treat the SPE pillar:
3) wild cabbage: 5g, adding concentration is 0.02 μ g/g, adds 10ml acetone earlier, and vibration 1h crosses anhydrous sodium sulphate and dewaters, and centrifuging and taking supernatant liquor 4ml dries up with nitrogen, finally uses the mixed solvent constant volume of 2ml acetonitrile/water=6: 5 (v/v), treats the SPE pillar.
According to wet method dress post, in 2ml acetone, (solid-phase extraction SPE) in the void column, adds corresponding sieve plate (aperture is 20 μ m), drains with vacuum pump to be filled into the 3ml Solid-Phase Extraction with 100mg MIP-HMDI or NIP-HMDI particles dispersed.Carry out the pre-leaching activation respectively with 2ml methyl alcohol and 2ml water earlier; Behind the last sample, select for use the mixed solvent of 2ml acetonitrile/water=6: 5 (v/v) to carry out drip washing, drain.Use 3ml acetone wash-out at last, collect elutriant, nitrogen dries up the back and is settled to 1ml with normal hexane, detects with the GC method.
Lambda-cyhalothrin sees Table 2 in the rate of recovery experimental result of such SPE post.From the result, the MIP-HMDI pillar obviously is better than the NIP-HMDI pillar to the concentration effect of lambda-cyhalothrin, and the rate of recovery can reach more than 85%, is applicable to the efficiently concentrating of trace lambda-cyhalothrin in environment and the plant sample.
Experiment 1-3:
The bonding properties life-span of polymkeric substance MIP-HMDI is investigated.Used MIP-HMDI is collected, use acetone ultrasonic extraction thorough washing again, do not detect lambda-cyhalothrin molecule (GC method) up to the washing lotion supernatant.Dry back is reusable, through SPE post rate of recovery experiment test, when recycling the 6th time, still can keep the lambda-cyhalothrin in the water sample there is 89.3% the rate of recovery, this has illustrated that this imprinted polymer has regenerability preferably, has remedied the not re-usable defectives of biological active materials such as antibody.
Embodiment 2:
Taking by weighing exsiccant beta-cyclodextrin 1.5mmol is dissolved among the anhydrous DMSO of 20mL, add 0.5mmol lambda-cyhalothrin (template molecule), room temperature (15～35 ℃) slowly drips the 9mmol Toluene-2,4-diisocyanate after stirring 1h down again, 4-vulcabond (TDI), 65 ℃ of lower magnetic force stirring reaction 24h; After reaction finishes, product solution is transferred in a large amount of acetone solvents repeatedly precipitating (250ml * 3), obtains white flocculent precipitate; White each solvent of flocculent precipitate reusable heat water-ethanol-acetone ultrasonic extraction successively (is not detected with GC) till the washing lotion supernatant detects template molecule to remove unreacted beta-cyclodextrin, linking agent, template molecule and DMSO; After centrifugal, suction filtration, the drying bulk polymer is ground to form fine particle, obtain with the crosslinked lambda-cyhalothrin MIP of TDI (being MIP-TDI), room temperature preservation is in dry vessel.
Make blank with NIP, its synthetic method is not except that adding the template molecule, and all the other steps are identical with the preparation method of above-mentioned lambda-cyhalothrin MIP, gets NIP-TDI.
Measure the particle meso-position radius of crosslinked MIP-TDI of this beta-cyclodextrin and NIP-TDI with the laser particle size distribution instrument, be respectively 21.53 μ m and 25.96 μ m.The absorption mean pore size of measuring MIP-TDI and NIP-TDI with the lacunarity analysis instrument is 14.6nm and 12.7nm, belongs to the mesopore rank, therefore helps the solute transmission, has improved the speed of polymer scale matched moulds plate molecule.
Experiment 2-1:
Investigate the bonding properties of this polymkeric substance by batch balance in conjunction with test: take by weighing one group of MIP-TDI/NIP-TDI 10mg respectively and place the 2mL centrifuge tube respectively to lambda-cyhalothrin, add the lambda-cyhalothrin solution of 1.5mL 5 μ g/mL, this solution is the mixed solvent of acetonitrile/water=6: 5 (v/v); The sealing back is room temperature vibration 2h in quiet mixing tank, and centrifugal then (8000rpm 10min), draws an amount of supernatant and crosses film (0.22 μ m organic membrane) back sample introduction, measures the Cf C of target analytes in the upper solution with the HPLC method
FreeFrom result's (seeing Table 1) as can be known, obviously greater than NIP-TDI, Δ Bound% is near 25% to the binding capacity of template molecule for MIP-TDI, and IF is about 3, and this explanation trace effect is better, and imprinted polymer has embodied higher special absorption property.
Experiment 2-2:
Select the blank sample of tap water, soil and wild cabbage respectively, add an amount of lambda-cyhalothrin standard substance stock solution (10 μ g/ml, normal hexane are solvent), specific as follows:
1) water sample: 5ml, adding concentration is 0.02 μ g/ml, directly treats the SPE pillar;
2) soil: 5g, adding concentration is 0.02 μ g/g, adds 10ml acetone and 2ml water earlier, vibration 1h crosses anhydrous sodium sulphate and dewaters centrifuging and taking supernatant liquor 4ml, dry up with nitrogen, finally use the mixed solvent constant volume of 2ml acetonitrile/water=6: 5 (v/v), treat the SPE pillar;
3) wild cabbage: 5g, adding concentration is 0.02 μ g/g, adds 10ml acetone earlier, and vibration 1h crosses anhydrous sodium sulphate and dewaters, and centrifuging and taking supernatant liquor 4ml dries up with nitrogen, finally uses the mixed solvent constant volume of 2ml acetonitrile/water=6: 5 (v/v), treats the SPE pillar.
According to wet method dress post, 100mg MIP-TDI or NIP-TDI particles dispersed in 2ml acetone, are filled in the 3mL SPE void column, add corresponding sieve plate (aperture is 20 μ m), drain with vacuum pump.Carry out the pre-leaching activation respectively with 2ml methyl alcohol and 2ml water earlier; Behind the last sample, select for use the mixed solvent of 2ml acetonitrile/water=6: 5 (v/v) to carry out drip washing, drain.Use 3ml acetone wash-out at last, collect elutriant, nitrogen dries up the back and is settled to 1mL with normal hexane, detects with the GC method.
Lambda-cyhalothrin sees Table 2 in the rate of recovery experimental result of such SPE post.From the result, the MIP-TDI pillar obviously is better than the NIP-TDI pillar to the concentration effect of lambda-cyhalothrin, and the rate of recovery can reach more than 85%, is applicable to the efficiently concentrating of trace lambda-cyhalothrin in environment and the plant sample.
Experiment 2-3:
The bonding properties life-span of polymkeric substance MIP-TDI is investigated.Used MIP-TDI is collected, use acetone ultrasonic extraction thorough washing again, do not detect lambda-cyhalothrin molecule (GC method) up to the washing lotion supernatant.Dry back is reusable, through SPE post rate of recovery experiment test, when recycling the 6th time, still can keep the lambda-cyhalothrin in the water sample there is 91.5% the rate of recovery, this has illustrated that this imprinted polymer has regenerability preferably, has remedied the not re-usable defectives of biological active materials such as antibody.
Embodiment 3:
Taking by weighing exsiccant beta-cyclodextrin 2mmol is dissolved among the anhydrous DMSO of 25mL, add 0.5mmol lambda-cyhalothrin template molecule, room temperature (15～35 ℃) slowly drips 10mmol naphthalene diisocyanate (NDI), 65 ℃ of lower magnetic force stirring reaction 24h after stirring 1h down again; After reaction finishes, take out white soup compound, to remove template molecule and unreacted beta-cyclodextrin, linking agent (NDI) and DMSO, till the washing lotion supernatant detects template molecule, (do not detect) with GC with acetone-hot water-ethanol ultrasonic extraction successively; After centrifugal, suction filtration, the drying bulk polymer is ground to form fine particle, obtain with the crosslinked lambda-cyhalothrin MIP of NDI (being MIP-NDI), room temperature preservation is in dry vessel.
Make blank with NIP, its synthetic method is not except that adding the template molecule, and all the other steps are identical with the preparation method of above-mentioned lambda-cyhalothrin MIP, gets NIP-NDI.
Measure the particle meso-position radius of crosslinked MIP-NDI of this beta-cyclodextrin and NIP-NDI with the laser particle size distribution instrument, be respectively 36.87 μ m and 35.41 μ m.The absorption mean pore size of measuring MIP-NDI and NIP-NDI with the lacunarity analysis instrument is 15.4nm and 13.9nm, belongs to the mesopore rank, therefore helps the solute transmission, has improved the speed of polymer scale matched moulds plate molecule.
Experiment 3-1:
Investigate the bonding properties of this polymkeric substance by batch balance in conjunction with test: take by weighing one group of MIP-NDI/NIP-NDI 10mg respectively and place the 2mL centrifuge tube respectively to lambda-cyhalothrin, add the lambda-cyhalothrin solution of 1.5mL 5 μ g/mL, this solution is the mixed solvent of acetonitrile/water=5: 6 (v/v); The sealing back is room temperature vibration 2h in quiet mixing tank, and centrifugal then (8000rpm 10min), draws an amount of supernatant and crosses film (0.22 μ m organic membrane) back sample introduction, measures the Cf C of target analytes in the upper solution with the HPLC method
FreeFrom result's (seeing Table 1) as can be known, obviously greater than NIP-NDI, Δ Bound% is about 25% to MIP-NDI to the binding capacity of template molecule, and IF reaches 2.8, and this explanation trace effect is better, and imprinted polymer has embodied higher special absorption property.
Experiment 3-2:
Select the blank sample of tap water, soil and wild cabbage respectively, add an amount of lambda-cyhalothrin standard substance stock solution (10 μ g/ml, normal hexane are solvent), specific as follows:
1) water sample: 5ml, adding concentration is 0.02 μ g/ml, directly treats the SPE pillar;
2) soil: 5g, adding concentration is 0.02 μ g/g, adds 10ml acetone and 2ml water earlier, vibration 1h crosses anhydrous sodium sulphate and dewaters centrifuging and taking supernatant liquor 4ml, dry up with nitrogen, finally use the mixed solvent constant volume of 2ml acetonitrile/water=6: 5 (v/v), treat the SPE pillar;
3) wild cabbage: 5g, adding concentration is 0.02 μ g/g, adds 10ml acetone earlier, and vibration 1h crosses anhydrous sodium sulphate and dewaters, and centrifuging and taking supernatant liquor 4ml dries up with nitrogen, finally uses the mixed solvent constant volume of 2ml acetonitrile/water=6: 5 (v/v), treats the SPE pillar.
According to wet method dress post, 100mg MIP-NDI or NIP-NDI particles dispersed in 2ml acetone, are filled in the 3mL SPE void column, add corresponding sieve plate (aperture is 20 μ m), drain with vacuum pump.Carry out the pre-leaching activation respectively with 2ml methyl alcohol and 2ml water earlier; Behind the last sample, select for use the mixed solvent of 2ml acetonitrile/water=6: 5 (v/v) to carry out drip washing, drain.Use 3ml acetone wash-out at last, collect elutriant, nitrogen dries up the back and is settled to 1mL with normal hexane, detects with the GC method.
Lambda-cyhalothrin sees Table 2 in the rate of recovery experimental result of such SPE post.From the result, the MIP-NDI pillar obviously is better than the NIP-NDI pillar to the concentration effect of lambda-cyhalothrin, and the rate of recovery can reach more than 85%, is applicable to the efficiently concentrating of trace lambda-cyhalothrin in environment and the plant sample.
Experiment 3-3:
The bonding properties life-span of polymkeric substance MIP-NDI is investigated.Used MIP-NDI is collected, use acetone ultrasonic extraction thorough washing again, do not detect lambda-cyhalothrin molecule (GC method) up to the washing lotion supernatant.Dry back is reusable, through SPE post rate of recovery experiment test, when recycling the 6th time, still can keep the lambda-cyhalothrin in the water sample there is 90.3% the rate of recovery, this has illustrated that this imprinted polymer has regenerability preferably, has remedied the not re-usable defectives of biological active materials such as antibody.
Each polymkeric substance of table 1 is to the bonding properties of template molecule
Each polymkeric substance of table 2-SPE pillar is to the rate of recovery of lambda-cyhalothrin
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. the preparation method of a lambda-cyhalothrin molecularly imprinted polymer is characterized in that may further comprise the steps successively:
1), will be dissolved in as the beta-cyclodextrin of function monomer in the solvent, add lambda-cyhalothrin then, stirring reaction 0.5～1.5h under the room temperature as template molecule; The mol ratio of described beta-cyclodextrin and lambda-cyhalothrin is 2～5: 1;
2), in the mixed solution of step 1) gained, add isocyanate ester compound, in 60～70 ℃ of magnetic agitation reaction 22～26h as linking agent; The mol ratio of described isocyanate ester compound and lambda-cyhalothrin is 10～30: 1;
3), to step 2) reaction product of gained adopts the washing of ultrasonic extraction method, to remove lambda-cyhalothrin, unreacted beta-cyclodextrin and isocyanate ester compound and solvent, till the washing lotion supernatant does not detect lambda-cyhalothrin;
4), with the step 3) gained through centrifugal, suction filtration, drying, the block superpolymer of gained grinds to form particle, described particle is the lambda-cyhalothrin molecularly imprinted polymer.
2. the preparation method of lambda-cyhalothrin molecularly imprinted polymer according to claim 1, it is characterized in that: described isocyanate ester compound is 1, hexamethylene-diisocyanate, benzene-2,4-vulcabond, Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond or naphthalene diisocyanate.
3. the preparation method of lambda-cyhalothrin molecularly imprinted polymer according to claim 2 is characterized in that: the solvent in the described step 1) is an anhydrous dimethyl sulfoxide.
4. the purposes of the lambda-cyhalothrin molecularly imprinted polymer for preparing as any one method in the claim 1～3 and get: be used for the high-selectivity enrichment and the separation and purification of environmental sample or plant sample trace lambda-cyhalothrin.
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| CN103214615A (en) * | 2013-04-09 | 2013-07-24 | 江苏大学 | Preparation method of rare earth doped fluorescent imprinted polymer |
| CN103351449A (en) * | 2013-04-11 | 2013-10-16 | 江苏大学 | Method for preparing porous magnetic imprinting absorption agent through emulsion polymerization |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473862A (en) * | 2002-05-10 | 2004-02-11 | 北京化工大学 | Print separating method of natural product with cyclodextrin molecule |
| WO2010029541A1 (en) * | 2008-09-09 | 2010-03-18 | Salio Nanotechnologies Ltd. | MOLECULARLY IMPRINTED SMART POLYMERS (MISPs) |
-
2010
- 2010-08-26 CN CN2010102681945A patent/CN101985493B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473862A (en) * | 2002-05-10 | 2004-02-11 | 北京化工大学 | Print separating method of natural product with cyclodextrin molecule |
| WO2010029541A1 (en) * | 2008-09-09 | 2010-03-18 | Salio Nanotechnologies Ltd. | MOLECULARLY IMPRINTED SMART POLYMERS (MISPs) |
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| CN103214615B (en) * | 2013-04-09 | 2015-03-04 | 江苏大学 | Preparation method of rare earth doped fluorescent imprinted polymer |
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| CN103881020A (en) * | 2014-03-20 | 2014-06-25 | 江苏大学 | Method for preparing molecularly imprinted polymer for fluorescence detection of cyhalothrin |
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| CN104892841B (en) * | 2015-05-19 | 2017-04-12 | 浙江大学 | Method for absorbing di-(2-ethylhexyl)phthalate via molecular imprinting technique |
| CN105399915A (en) * | 2015-12-18 | 2016-03-16 | 天津医科大学 | Aesculin sustained and controlled release molecular imprinting skeletal material, and preparation method thereof |
| CN105399915B (en) * | 2015-12-18 | 2017-12-12 | 天津医科大学 | Aesculin delays controlled release molecular engram framework material and preparation method thereof |
| CN108993442A (en) * | 2018-07-25 | 2018-12-14 | 上海理工大学 | A kind of preparation method of the molecular imprinted polymer on surface with high-adsorption-capacity |
| CN109212008A (en) * | 2018-10-17 | 2019-01-15 | 西北农林科技大学 | Detect the electrochemical sensor preparation method and its measuring method of anabasine pesticide |
| CN109212008B (en) * | 2018-10-17 | 2020-12-22 | 西北农林科技大学 | Preparation method and determination method of electrochemical sensor for detecting neonicotinoid pesticides |
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